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RESEARCH PAPER · Journal of the American Chemical Society · 2020

[ABa2Cl][Ga4S8] (A = Rb, Cs): Wide-Spectrum Nonlinear Optical Materials Obtained by Polycation-Substitution-Induced Nonlinear Optical (NLO)-Functional Motif Ordering

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[ABa2Cl][Ga4S8] (A = Rb, Cs): Wide-Spectrum Nonlinear Optical Materials Obtained by Polycation-Substitution-Induced Nonlinear Optical (NLO)-Functional Motif OrderingOriginalA new type of novel salt-inclusion chalcogenide with ultralow thermal conductivity14New quaternary chalcogenide Ba 4 HgAs 2 S 10 originating from the combination of linear [HgS 2 ] 2− and tetrahedral [AsS 4 ] 3− modules8Salt-inclusion chalcogenides: an emerging class of IR nonlinear optical materials54Similarities and differences between Mn( ii ) and Zn( ii ) coordination polymers supported by porphyrin-based ligands: synthesis, structures and nonlinear optical properties24Second-order nonlinear optical-active selenide borate Zn8Se2(BO2)12: Experimental and theoretical analysis9Ba2[MoO3(OH)(IO3)2]IO3: A Promising SHG Material Featuring a Λ-Shaped Functional Motif Achieved by Universal Mono-Site Substitution50Salt-Inclusion Chalcogenide [Ba4Cl2][ZnGa4S10]: Rational Design of an IR Nonlinear Optical Material with Superior Comprehensive Performance Derived from AgGaS2134Pb 18 O 8 Cl 15 I 5 : A Polar Lead Mixed Oxyhalide with Unprecedented Architecture and Excellent Infrared Nonlinear Optical Properties165Pb18O8Cl15I5: A Polar Lead Mixed Oxyhalide with Unprecedented Architecture and Excellent Infrared Nonlinear Optical Properties29Recent Advances in Oxide‐based Nonlinear Optical Materials with Wide Infrared Transparency Beyond 6 μm38Two Mixed-Anion Units of [GeOSe3] and [GeO3S] Originating from Partial Isovalent Anion Substitution and Inducing Moderate Second Harmonic Generation Response and Large Birefringence55AMnAs3S6 (A = Cs, Rb): Phase-Matchable Infrared Nonlinear Optical Functional Motif [As3S6]3– Obtained via Surfactant–Thermal Method32Phase Matching, Strong Frequency Doubling, and Outstanding Laser-Induced Damage Threshold in the Biaxial, Quaternary Diamond-like Semiconductor Li 4 CdSn 2 S 779α-CdP2: Large SHG Effect Originating from the Synergism of Parallel ∞1[P–] Polyanion Chains and Distorted CdP4 Tetrahedra21From AgGaS 2 to AgHgPS 4 : vacancy defects and highly distorted HgS 4 tetrahedra double-induced remarkable second-harmonic generation response67A novel promising infrared nonlinear optical selenide KAg 3 Ga 8 Se 14 designed from benchmark AgGaQ 2 (Q = S, Se)55Investigation of the second-order nonlinear optical property of Sr6Sb6S173Chiral Template‐Driven Macroscopic Chirality Control: Structure‐Second‐Harmonic Generation Properties Relationship24Recent Achievements in Lone-Pair Cation-Based Infrared Second-Order Nonlinear Optical Materials95[GaF(H 2 O)][IO 3 F]: a promising NLO material obtained by anisotropic polycation substitution42Ba 2 Ge 2 Te 5 : a ternary NLO-active telluride with unusual one-dimensional helical chains and giant second harmonic-generation tensors31Balanced infrared nonlinear optical performance achieved by modulating the covalency and ionicity distributions in the electron localization function map42Cu 4 MnGe 2 S 7 and Cu 2 MnGeS 4 : two polar thiogermanates exhibiting second harmonic generation in the infrared and structures derived from hexagonal diamond22From thiophosphate to chalcohalide: mixed-anion AgS x Cl y ligands concurrently enhancing nonlinear optical effects and laser-damage threshold10La 6 Cd 0.75 Ga 2 Q 11.5 Cl 2.5 (Q = S and Se): two new nonlinear optical chalcohalides with a large laser-induced damage threshold15M 6 PS 5 X (M = Ag, Cu; X = Cl, Br) chalcohalides exhibiting strong nonlinear optical responses and high laser damage resistances9Na 2 GaS 2 Cl: a new sodium-rich chalcohalide with two-dimensional [GaS 2 ] ∞ layers and wide interlayer space15Na 4 SnS 4 and Na 4 SnSe 4 exhibiting multifunctional physicochemical performances as potential infrared nonlinear optical crystals and sodium ion conductors27UV-vis/X-ray/thermo-induced synthesis and UV–SWIR photoresponsive property of a mixed-valence viologen molybdate semiconductor25Na 6 MQ 4 (M=Zn, Cd; Q=S, Se): Promising New Ternary Infrared Nonlinear Optical Materials24Second-order nonlinear optical and photoelectric properties of Zn4B6O12S20A Series of Pentanary Salt-Inclusion Chalcogenoborates Containing a B12Q12 (Q = S, Se) Cluster Exhibiting a Kleinman-Forbidden Frequency-Doubling Effect25Quaternary Chalcohalides CdSnSX2 (X = Cl or Br) with Neutral Layers: Syntheses, Structures, and Photocatalytic Properties18Introduction of Li into Ag-Based Noncentrosymmetric Sulfides for High-Performance Infrared Nonlinear Optical Materials40Uncovering a Functional Motif of Nonlinear Optical Materials by In Situ Electron Density and Wavefunction Studies Under Laser Irradiation39Uncovering a Functional Motif of Nonlinear Optical Materials by In Situ Electron Density and Wavefunction Studies Under Laser Irradiation1Atomically precise metal chalcogenide supertetrahedral clusters: frameworks to molecules, and structure to function79ASb5S8 (A = K, Rb, and Cs): Thermal Switching of Infrared Nonlinear Optical Properties across the Crystal/Glass Transformation39AXHg3P2S8 (A = Rb, Cs; X = Cl, Br): New Excellent Infrared Nonlinear Optical Materials with Mixed‐Anion Chalcohalide Groups of Trigonal Planar [HgS2X]3− and Tetrahedral [HgS3X]5−58Hydrogen‐Bond‐Driven Synergistically Enhanced Hyperpolarizability: Chiral Coordination Polymers with Nonpolar Structures Exhibiting Unusually Strong Second‐Harmonic Generation87Hydrogen‐Bond‐Driven Synergistically Enhanced Hyperpolarizability: Chiral Coordination Polymers with Nonpolar Structures Exhibiting Unusually Strong Second‐Harmonic Generation19Cs2ZnSn3S8: A Sulfide Compound Realizes a Large Birefringence by Modulating the Dimensional Structure24Sr2Pb(BeB5O10)(BO3): An Excellent Ultraviolet Nonlinear-Optical Beryllium Borate by the Pb-Modified Construction of a Conjugated System and Lone-Pair Effect14Mg 2 In 3 Si 2 P 7 : A Quaternary Diamond-like Phosphide Infrared Nonlinear Optical Material Derived from ZnGeP 2130Solvothermal Syntheses of Three-Dimensional Open-Framework Thioantimonates Displaying Nonlinear Optical Responses5Li 4 MgGe 2 S 7 : The First Alkali and Alkaline‐Earth Diamond‐Like Infrared Nonlinear Optical Material with Exceptional Large Band Gap213Li4MgGe2S7: The First Alkali and Alkaline‐Earth Diamond‐Like Infrared Nonlinear Optical Material with Exceptional Large Band Gap15A Congruent‐Melting Mid‐Infrared Nonlinear Optical Vanadate Exhibiting Strong Second‐Harmonic Generation22A Congruent‐Melting Mid‐Infrared Nonlinear Optical Vanadate Exhibiting Strong Second‐Harmonic Generation63Hg 3 P 2 S 8 : A New Promising Infrared Nonlinear Optical Material with a Large Second-Harmonic Generation and a High Laser-Induced Damage Threshold111The Rise of Infrared Nonlinear Optical Pnictides: Advances and Outlooks36Cd3(PO4)(TePO6): A Novel Cadmium Tellurite‐Phosphate featuring a {[TePO6]3−}∞ Chain15Constructing a simple Cone–Chain motif to significantly enhance the first hyperpolarizability of horn-shaped carbon nanocones0H{[Na(H2O)3]6F}(PO4)2 ⋅ 2(H2O): A New Polycation‐Type Phosphate with Deep Ultraviolet Transparency0Superior Infrared Nonlinear Optical Performance Achieved by Synergetic Functional Motif and Vacancy Site Modulations48Ca3(TeO3)2(MO4) (M = Mo, W): Mid-Infrared Nonlinear Optical Tellurates with Ultrawide Transparency Ranges and Superhigh Laser-Induced Damage Thresholds46Investigation into Structural Variation from 3D to 1D and Strong Second Harmonic Generation of the AHgPS4 (A+ = Na+, K+, Rb+, Cs+) Family26Stable 3D neutral gallium thioantimonate frameworks decorated with transition metal complexes for a tunable photocatalytic hydrogen evolution9Rational Crystal Structure Design and Nonlinear-Optical Properties of Noncentrosymmetric RbCu2NbS47Structural modification from centrosymmetric Rb 4 Hg 2 Ge 2 S 8 to noncentrosymmetric (Na 3 Rb)Hg 2 Ge 2 S 8 : mixed alkali metals strategy for infrared nonlinear optical material design28Sn7Br10S2: The First Ternary Halogen‐Rich Chalcohalide Exhibiting a Chiral Structure and Pronounced Nonlinear Optical Properties24Sn7Br10S2: The First Ternary Halogen‐Rich Chalcohalide Exhibiting a Chiral Structure and Pronounced Nonlinear Optical Properties145[ASr 4 Cl][Ge 3 S 10 ] (A = Na, K) and [KBa 4 Cl][Ge 3 S 10 ]: new salt-inclusion infrared nonlinear optical crystals with zero-dimensional [Ge 3 S 9 ] clusters32A 2 P 2 S 6 (A = Ba and Pb): a good platform to study the polymorph effect and lone pair effect to form an acentric structure28A 2 Zn 3 P 4 S 13 (A = Rb and Cs): First Infrared Nonlinear Optical Materials with Mixed Thiophosphate Functional Motifs PS 4 and P 2 S 621AAg 2 PS 4 (A = K, Na/K): the first-type of noncentrosymmetric alkali metal Ag-based thiophosphates exhibiting excellent second-order nonlinear optical performances21AAg 3 Ga 8 Se 14 (A = Rb, Cs): second-harmonic generation responses realized through the parallel arrangement of AgSe 4 and GaSe 4 tetrahedrons5Achieving a strong second harmonic generation response and a wide band gap in a Hg-based material41AIn 4 S 6 Cl (A = Rb and Cs) and Pb 5 Sn 3 Q 10 Cl 2 (Q = S and Se): quaternary chalcohalides with mixed anionic coordination exhibit photocurrent responses11Broad transparency and wide band gap achieved in a magnetic infrared nonlinear optical chalcogenide by suppressing d–d transitions41Chiral coordination compounds with exceptional enantioselectivity10First polar quaternary sulphide CsLiGa 6 S 10 with mixed ordered alkali cations displaying excellent infrared nonlinear optical properties16From oxides to oxysulfides: the mixed-anion GeS 3 O unit induces huge improvement in the nonlinear optical effect and optical anisotropy for potential nonlinear optical materials19KAg3Ga8S14: An Mid- and Far-infrared Nonlinear Optical Material Exhibiting High Laser-induced Damage Threshold※3KNa 0.78 Eu 0.27 In 3.80 B 12 S 12 : a novel hexanary thioborate featuring a B 12 S 12 cluster and diverse InS x ( x = 4, 5, 6) units9Li-Free ternary sulphide Cs 5 Ga 9 S 16 with excellent nonlinear optical performance similar to classic LiGaS 213Metal oxyhalides: an emerging family of nonlinear optical materials124Na 4 Ga 8 S 14 : a Ga-enriched wide band gap ternary alkali-metal sulfide with unique [Ga 12 S 42 ] 12-membered rings2The exploration of new infrared nonlinear optical crystals based on the polymorphism of BaGa 4 S 731The synthesis and structure–property relation analysis of metal chalcohalide crystals Cs 2 InPS 4 X 2 (X = Cl, Br) with mixed anions6Wide band gap thiophosphates ASrPS 4 (A = Li, Na, K, Rb, Cs): cation size effect induced successive structural transformation13A new salt-inclusion chalcogenide exhibiting distinctive [Cd11In9S26]3− host framework and decent nonlinear optical performances16Optimizing the Nonlinear Optical Performance of an A-N-M-Q (A: Alkali Metal; N: d10 Metal; M: Main Group Metal; Q: Chalcogen) System44Pb 4 SeBr 6 : A Congruently Melting Mid‐Infrared Nonlinear Optical Material with Excellent Comprehensive Performance39Infrared nonlinear optical performances of a new sulfide β-PbGa2S415Material research from the viewpoint of functional motifs103Nonlinear optical and detonation properties of semiorganic nitrate crystal C6H14N2(NO3)3·H3O8Synthesis, Crystal and Electronic Structures, and Nonlinear Optical Properties of Y4Si3S1212Uncovering a Vital Band Gap Mechanism of Pnictides49The Kurtz-Perry powder technique revisited: A case study on the importance of reference quality and broadband nonlinear optical measurements using LiInSe232Rb2FeGe3S8 and Cs2FeGe3S8: New layered chalcogenides in A2MIIMIV3Q8 family with antiferromagnetic property6BaSi7P10 and SrSi7P10: Two Infrared Nonlinear Optical Phosphides with T2 Supertetrahedra Exhibiting Strong Second‐Harmonic Generation Effects22SrAgAsS4: A Noncentrosymmetric Sulfide with Good Infrared Nonlinear Optical Performance Induced by Aliovalent Substitution from Centrosymmetric SrGa2S412AgGaSe2-Inspired Nonlinear Optical Materials: Tetrel Selenides of Alkali Metals and Mercury34Additive‐Triggered Polar Polymorph Formation: β‐Sc(IO 3 ) 3 , a Promising Next‐Generation Mid‐Infrared Nonlinear Optical Material42Additive‐Triggered Polar Polymorph Formation: β‐Sc(IO3)3, a Promising Next‐Generation Mid‐Infrared Nonlinear Optical Material3AgGaGeSe4: An Infrared Nonlinear Quaternary Selenide with Good Performance6[Ba2F2][Ge2O3S2]: An Unprecedented Heteroanionic Infrared Nonlinear Optical Material Containing Three Typical Anions47Synthesis, characterization and theoretical calculations of four chiral schiff base materials for second harmonic generation applications7(Na0.74Ag1.26)BaSnS4: A New AgGaS2‐Type Nonlinear Optical Sulfide with a Wide Band Gap and High Laser Induced Damage Threshold14Mixed-Anion-Oriented Design of LnMGa3S6O (Ln = La, Pr, and Nd; M = Ca and Sr) Nonlinear Optical Oxysulfides with Targeted Property Balance56[Cs6Cl][Ga5GeQ12] (Q = S, Se): two novel porous layered chalcohalides exhibiting two-band emission and ion exchange properties6Ag4SnGe2S7: A Noncentrosymmetric Chalcogenide in I4–II–IV2–VI7 System with Non-Diamond-Like Structure Featuring 1D ∞[SnGe2S8]6– Infinite Chain2Ternary AGa5S8 (A = K, Rb, Cs): Promising infrared nonlinear optical materials rationally realized by “one-for-multiple substitution” strategy37Chalcohalides: A Rising Type of Second‐Order Nonlinear Optical Materials28Isoreticular Design of KTiOPO 4 -Like Deep-Ultraviolet Transparent Materials Exhibiting Strong Second-Harmonic Generation68Ag[SC(NH2)2]2F: A Laser Damage-Tolerant Infrared Nonlinear Optical Material9Syntheses, structures, and characterization of new heteroanionic chalcohalides: Na2Ba17In8Q21F18 (Q = S, Se), KBa2InQ3F2 (Q = S, Se)5Rb 2 CdSi 4 S 10 : novel [Si 4 S 10 ] T2-supertetrahedra-contained infrared nonlinear optical material with large band gap79Ag-based chalcogenides and derivatives as promising infrared nonlinear optical materials90The Antiperovskite‐Type Oxychalcogenides Ae3Q[GeOQ3] (Ae = Ba, Sr; Q = S, Se) with Large Second Harmonic Generation Responses and Wide Band Gaps68Enhanced Second-Harmonic-Generation Response in a KH2PO4-Type Calcium Nitrate Carboxylate with Unusual Three-Dimensional Inorganic and Organic Connections3KREP2Se6 (RE = Sm, Gd, Tb): The First Rare‐Earth Selenophosphates with Remarkable Nonlinear Optical Activities Realized by Synergistic Effect of RE‐ and P‐Based Motifs39Ba5Ga2SiO4S6: a Phase-Matching Nonlinear Optical Oxychalcogenide Design via Structural Regulation Originated from Heteroanion Introduction25Oxychalcogenides: A Promising Class of Materials for Nonlinear Optical Crystals with Mixed‐Anion Groups35AIn 3 Si 4 P 9 (A = Ca, Sr): quaternary phosphides with double-helix structures exhibiting high laser-induced damage thresholds19[Ba 4 X][In 19 S 32 ] (X = Cl, Br): two quaternary metal chalcohalides exhibiting remarkable photocurrent responses1[Sr 4 Cl 2 ][Si 3 S 9 ]: Ultrawide-bandgap salt-inclusion thiosilicate nonlinear optical material with unprecedented tri-polymerized [Si 3 S 9 ] clusters21A new infrared nonlinear optical material BaZnGeS 4 with a wide band gap and large nonlinear optical response34A non-centrosymmetric chalcohalide synthesized through the combination of chemical tailoring with aliovalent substitution12A wheel-shaped gallium-sulfide molecular ring with enhanced photocatalytic activity via indium alloying11Breaking the bottleneck of simultaneously wide band gap and large nonlinear optical coefficient by a “pore reconstruction” strategy in a salt-inclusion chalcogenide26Efficient and selective photocatalytic CO 2 reduction over Ga single atom decorated quantum dots under visible light16Open honeycomb frameworks of sulphides AHg 4 Ga 5 S 12 (A = Rb, Cs) exhibiting infrared nonlinear optical properties12Recent progress on sulfide infrared nonlinear optical materials with large SHG response and wide band gap26Significant increase of the photoresponse range and conductivity for a chalcogenide semiconductor by viologen coating through charge transfer10Solvent-free synthesis of magnesium phosphite-oxalates that show second-harmonic generation responses5The first polyanion-substitution-driven centrosymmetric-to-noncentrosymmetric structural transformation realizing an excellent nonlinear optical supramolecule [Cd 4 P 2 ][CdBr 4 ]17The first quaternary rare-earth oxythiogermanate with second-harmonic generation and ferromagnetic behavior26Toward Large Second-Harmonic Generation and Deep-UV Transparency in Strongly Electropositive Transition Metal Sulfates112K2CdGe3S8: A New Infrared Nonlinear Optical Sulfide6LnLiSiS4 (Ln = La and Ce): Promising infrared nonlinear optical materials designed by aliovalent substitution from SrCdSiS437Tunable Salt-Inclusion Chalcogenides for Ion Exchange, Photoluminescence, and Scintillation12Salt-inclusion chalcogenides: Double functional moieties design strategy toward excellent nonlinear optical materials12Recent progress in the design of IR nonlinear optical materials by partial chemical substitution: Structural evolution and performance optimization133Rational Design of a Rare‐Earth Oxychalcogenide Nd3[Ga3O3S3][Ge2O7] with Superior Infrared Nonlinear Optical Performance64Recent advances in non-π-conjugated nonlinear optical sulfates with deep-UV absorption edge53[K2PbX][Ga7S12] (X = Cl, Br, I): The First Lead‐Containing Cationic Moieties with Ultrahigh Second‐Harmonic Generation and Band Gaps Exceeding the Criterion of 2.33 eV46Zn2BS3Br: An Infrared Nonlinear Optical Material with Significant Dual-Property Enhancements Designed through a Template Grafting Strategy20Host–Guest Symmetry Matching in Two Crystalline Magnesium Sulfate Oxalates Obtained Via a Solvent-Free Route8Optimal Design of Mid-Infrared Nonlinear-Optical Crystals: From SrZnSnSe 4 to SrZnSiSe 422Ultrafast Nonlinear Optical Activities of Near-Infrared Aza-BODIPY Derivatives1Nonlinear Optical Sulfides LiMGa8S14 (M = Rb/Ba, Cs/Ba) Created by Li+ Driven 2D Centrosymmetric to 3D Noncentrosymmetric Transformation20Na3SiS3F: A Wide Bandgap Fluorothiosilicate with Unique [SiS3F] Unit and High Laser‐Induced Damage Threshold39Host–Guest Symmetry and Charge Matching in Glycine-Templated Metal Sulfate–Oxalates Obtained by a Solvent-Free Method9Recent advances in IR nonlinear optical chalcogenides with well-balanced comprehensive performance56Cs4Zn5P6S18I2: the Largest Birefringence in Chalcohalide Achieved by Highly Polarizable Nonlinear Optical Functional Motifs21Zn 2 HgP 2 S 8 : A Wide Bandgap Hg‐Based Infrared Nonlinear Optical Material with Large Second‐Harmonic Generation Response75Quadruple‐Bidentate Nitrate‐Ligated A 2 Hg(NO 3 ) 4 (A=K, Rb): Strong Second‐Harmonic Generation and Sufficient Birefringence59Quadruple‐Bidentate Nitrate‐Ligated A 2 Hg(NO 3 ) 4 (A=K, Rb): Strong Second‐Harmonic Generation and Sufficient Birefringence2

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